Method of Preparing OPTO-Electronic Device

ABSTRACT

A method is provided to produce an opto-electronic device comprising a substrate, a first electrode layer, a second electrode layer of opposite polarity to said first electrode layer, any interlayers and, between said first and second electrode layers, a first functional material in interfacial contact with a second functional material, wherein the first functional material has the structure of a laterally porous film and the second functional material is a film disposed over and interpenetrating with the film of the first functional material.

This invention relates to methods of preparing opto-electronic devicessuch as photovoltaic (PV), photodetector, and organic light emittingdiode (OLED) devices, in particular to methods to produce a largesurface area interface between two functional layers of materials inthese devices, such that each of the two layers of materials has acontinuous non-tortuous exciton or electron/hole charge percolation pathfrom the interface to its other surface without the presence of islandsof material from one layer within the material of the other layer.

In opto-electronic devices such as PV and OLED devices, functionallayers are sandwiched between an anode layer, generally of indium tinoxide (ITO) on a glass or polymer substrate, and a low work-functioncathode layer such as aluminium/lithium fluoride. The functional layersinclude an electroluminescent or light-absorbing layer, and may includea hole transport layer and/or an electron transport layer. In thesedevices, charge carriers (electrons or holes) are transported to or fromthe electroluminescent or light-absorbing layer through a hole transportlayer and/or an electron transport layer, from or to the cathode andanode layers. More specifically, charge carriers injected into anelectroluminescent layer or generated by a light-absorbing layer willtravel to or from the interface between the light-active layer and ahole transport layer or an electron transport layer, from or towards therelevant electrode at the other surface of the hole transport layer oran electron transport layer.

In general, the functional materials are deposited as layers over oneelectrode on a substrate, and the cell is completed by depositing theother electrode over the functional layers. Bi-layers of organicmaterials have been used for PV applications, for example a bi-layer ofa light absorbing layer over a hole transporting layer. However, thebi-layer structure, in which the interface between the two layers isessentially planar, results in low quantum efficiencies, due to thesmall interfacial area existing between the two functional organicmaterials, and the mismatch between the typical exciton range and thethickness of polymer required to absorb most of the light.

Polymer blends have been used for organic PV and OLED applications.However, the blended structure, in which the two functional materials ofthe blend exist as separate but interdispersed phases, can also resultin low quantum efficiencies despite the large interfacial contactbetween the two phases, due to the structure presenting long, tortuouspercolation paths for exciton or electron/hole charges to travel totheir collecting or source electrodes.

It would therefore be desirable to produce, in an opto-electronic devicesuch as an organic PV device or an OLED device, an interface betweenbi-phasic functional layer materials that can provide not only anincreased interfacial area compared with a bi-layered structure, butthat also can present a shorter, less tortuous charge percolation pathcompared with a blended structure.

The present invention therefore provides a structure that isintermediate between the bi-layer and blend morphologies. Thisintermediate structure possesses both a large interfacial area betweenthe material phases and simple non-tortuous percolation paths forexcitons or electron/hole charges.

Waiheim et al., Science, 1999, vol. 283, p520-522 discloses a techniquefor creating nanoporous polymer films for use as anti-reflective opticalcoatings, by spin-coating a polymer blend of polystyrene (PS) andpolymethyl methacrylate (PMMA), both dissolved in tetrahydrofuran, andevaporating the solvent to provide a polymer film exhibiting lateralphase morphology, followed by exposing the film to a selective solventcyclohexane to selectively dissolve and remove the PS component to leavea laterally porous PMMA film exhibiting a specific optical property i.e.a low refractive index. The present invention uses this and similartechniques based on controlled nanoscale phase separation, for thepreparation of opto-electronic devices.

Consequently, the present invention enables the preparation ofopto-electronic devices such as organic PV devices and OLED devices withcontrolled nanoscale phase separation that can exhibit greater devicequantum efficiencies than corresponding devices that use bi-layered orblended structures

The intermediate structure is formed by a laterally porous film of afirst functional material such as a hole transporting material and afilm of a second functional material such as a light-active materialdisposed over and interpenetrating with the film of the first functionalmaterial. In accordance with the methods of the invention, the firstfunctional material is so formed as to provide a topographically rough,laterally porous surface to be coated with the film of the secondfunctional material. When the second functional material is depositedover the surface of the first functional material, the second functionalmaterial enters the pores in the first functional material, and thetroughs between the peaks of the first functional material, so as toform a complementary film over and interpenetrating with the film of thefirst functional material. The topographically rough interface betweenthe first functional material and the second functional materialprovides a large contact area between the phases of the first and secondfunctional materials, and simple non-tortuous percolation paths forexcitons or electron/hole charges between the interface and the otherrespective surfaces of the first and second functional materials.

The invention has application in the fabrication of organic or hybrid(organic-inorganic) photovoltaic and photodetector devices, as well asother organic or hybrid opto-electronic devices.

According to the methods of the invention, a blend of a forming materialas a first blend material, and a second blend material that isimmiscible with the forming material, is deposited onto an electrodelayer on a substrate. The second blend material may be the firstfunctional material that is desired to be present in the final device,or may be a second forming material that will be removed and replaced bya functional material at a later stage of the process. In both cases,the forming material in the blend is specifically selected, depending onthe second blend material, to give the desired phase separation so thatthe forming material and the second blend material separate into alaterally phase separated film stricture of the forming material in afirst phase and of the second blend material in a second phase.Moreover, the forming material in the blend is specifically selected sothat any islands that may be formed, of one of the phases in the otherof the phases, are islands of the second blend material within theforming material. Thus, when the forming material is later removed, theislands of the second blend material will also be removed with theforming material phase, so as to leave a pure phase of the second blendmaterial. The phase separation scale may be controlled by appropriateselection of molecular weight of the forming material, solvent(s) forthe blend materials, and deposition conditions.

The removal of the forming material, and of any islands therein, leavesa laterally porous, pure film of the second blend material.

In the case that the second blend material is a first functionalmaterial, the porous film may be used directly to form theopto-electronic device by depositing on it a second functional material.Alternatively, in the case that the second blend material is a secondforming material, the porous film may be used as a template for thefunctional materials and thus employed indirectly to form theopto-electronic device.

Accordingly, in a first aspect, the present invention provides a methodof preparing an opto-electronic device comprising a substrate, a firstelectrode layer, a second electrode layer of opposite polarity to saidfirst electrode layer and, between said first and second electrodelayers, a first functional material in interfacial contact with a secondfunctional material, said method comprising:

forming the first electrode layer on the substrate;

depositing a blend of a first forming material and a curable firstfunctional material on said first electrode layer on said substrate toform a film, the first forming material and first functional materialbeing selected to separate into a laterally phase separated filmstructure wherein the first forming material phase optionally containsislands of the first functional material phase;

treating said laterally phase separated film structure so as to curesaid first functional material phase followed by removing the firstforming material phase and said optionally contained islands of thefirst functional material phase, or removing the first forming materialphase and said optionally contained islands of the first functionalmaterial phase from said laterally phase separated film structurefollowed by treating so as to cure said first functional material phase,to leave a cured, laterally porous film of said first functionalmaterial;

depositing a second functional material over and into the pores of saidcured, laterally porous film of the first functional material, so as toprovide a film of the second functional material over andinterpenetrating with the film of the first functional material; and

forming the second electrode layer over said film of the secondfunctional material.

In a second aspect, the present invention provides a method of preparingan opto-electronic device comprising a substrate, a first electrodelayer, a second electrode layer of opposite polarity to said firstelectrode layer and, between said first and second electrode layers, afirst functional material in interfacial contact with a secondfunctional material, said method comprising:

forming the first electrode layer on the substrate;

depositing a blend of a first forming material and a second formingmaterial on said first electrode layer on said substrate to form a film,the first forming material and second forming material being selected toseparate into a laterally phase separated film structure wherein thefirst forming material phase optionally contains islands of the secondforming material phase;

removing the first forming material phase and said optionally containedislands of the second forming material phase, to leave a laterallyporous film of said second forming material;

depositing a curable first functional material over and into the poresof said laterally porous film of the second forming material, so as toprovide a film of the first functional material over andinterpenetrating with the film of the second forming material;

treating said interpenetrating films of the second forming and firstfunctional materials so as to cure said first functional material phasefollowed by removing the second forming material and any uncuredportions of the first functional material, or removing the secondforming material and any uncured portions of the first functionalmaterial from said interpenetrating films of the second forming andfirst functional materials followed by treating so as to cure said firstfunctional material phase, to leave a cured, laterally porous film ofsaid first functional material;

depositing a second functional material over and into the pores of saidcured, laterally porous film of the first functional material, so as toprovide a film of the second functional material over andinterpenetrating with the film of the first functional material; and

forming the second electrode layer over said film of the secondfunctional material.

In a preferred embodiment of the second aspect, the second formingmaterial is UV-absorbent and the first functional material isUV-curable, and the treatment so as to cure said first functionalmaterial phase is by irradiating the interpenetrating films of thesecond forming and first functional materials with U radiation throughthe substrate, whereby portions of the first functional material exposedto the UV radiation and not masked by the second forming material arecured and portions of the first functional material unexposed to the UVradiation or masked by the second forming material remain uncured.

In a third aspect, the present invention provides an opto-electronicdevice comprising a substrate, a first electrode layer, a secondelectrode layer of opposite polarity to said first electrode layer and,between said first and second electrode layers, a first functionalmaterial in interfacial contact with a second functional material,wherein the first functional material has the structure of a laterallyporous film and the second functional material is a film disposed overand interpenetrating with the film of the first functional material.

By ‘laterally phase separated’ as used herein is meant that the twoprincipal phases co-exist such that the interface between the phases isessentially perpendicular to the plane of the film, which plane extendsin the lateral direction. Thus, if the plane of the film extendslaterally in the x and y directions, the interface between the phasesextends essentially in the z direction so as to separate the phasesacross the lateral plane of the film. For example, one of the phases mayexist as a plurality of separate and/or interconnected rod, ribbonand/or columnar structures that have their long axes orientedsubstantially normal to plane of the film, or may exist as a continuousphase containing a plurality of separate and/or interconnected rod-,ribbon- and/or column-shaped pores that have their long axes orientedsubstantially normal to plane of the film, with the space(s) betweenthese structures and/or within the pores being constituted by the otherof the two principal phases. Thus, the other of the two principal phasesmay also exist as a plurality of separate and/or interconnected rod,ribbon and/or columnar structures that have their long axes orientedsubstantially normal to plane of the film, or may exist as a continuousphase containing a plurality of separate and/or interconnected rod-,ribbon- and/or column-shaped pores that have their long axes orientedsubstantially normal to the plane of the film, with the space betweenthese structures and/or within the pores being constituted by the one ofthe two principal phases.

Accordingly, by ‘laterally porous film’ as used herein is meant a filmthat has within it a plurality of separate and/or interconnected rod-,ribbon- and/or column-shaped pores or dimples that have their long axesoriented substantially normal to plane of the film, and/or that has onit a plurality of separate and/or interconnected rod-, ribbon- and/orcolumn-shaped projections that have their long axes orientedsubstantially normal to plane of the film, such that the surfacesdefined by the pores, dimples and/or projections is essentiallyperpendicular to the plane of the film, which plane extends in thelateral direction. Thus, if the plane of the laterally porous filmextends laterally in the x and y directions, the surfaces defined by thepores, dimples and/or projections extend essentially in the z directionso as to separate the pores, dimples and/or projections across thelateral plane of the film.

The rod, ribbon and columnar structures in the laterally phase separatedstructures, and the rod-, ribbon- and column-shaped pores, dimples andprojections of the laterally porous films, may be irregular in size andshape in cross-section, and may vary in cross-sectional size and shapeover their axial extents. These rod, ribbon and columnar structures andpores, dimples and projections preferably have their axes spaced apart(in any cross-section in the plane of the film) by a distance in therange from 1 nm to 100 nm, more preferably in the range from 5 nm to 50nm. The average size in cross-section of the rod, ribbon and columnarstructures and pores, dimples and projections (in any cross-section inthe plane of the film) preferably is in the range from 1 nm to 100 nm,more preferably in the range from 5 nm to 50 nm.

In a preferred embodiment, the device is an electroluminescent or OLEDdevice, the first functional material is a charge transporting material,the second functional material is an electroluminescent material, thefirst electrode layer is the anode and the second electrode layer is thecathode.

In another preferred embodiment, the device is a photovoltaic device,the first functional material is a hole transporting material, thesecond functional material is an electron transporting material, thefirst electrode layer is the anode and the second electrode layer is thecathode.

The methods of the invention require a phase separation that is socontrolled as to produce a topographically highly featured interfacebetween the phases of the blend. Suitable techniques include thosedisclosed in Walheim et al., Science, 1999, vol. 283, p520-522. Thephase separation over the desired length scale can be controlled to thisend by an appropriate selection of molecular weights for the polymersforming the blend, to provide a lateral gap between formed phasefeatures of, for example, 10 to 25 nm. The film preferably has athickness between the length scale of the lateral phase separation andthe desired device thickness, for example a ratio of thickness to lengthscale of around 5:1-20:1.

The blend of first and second blend materials, in a suitable solvent,may be deposited by conventional techniques such as spin-coating,spray-coating, dip-coating, inkjet printing, screen printing, gravureprinting, or flexographic printing. The solvent is removed, e.g. byevaporation, to leave a blend film having laterally phase separatedmorphology.

The curable second blend material is curable preferably by thermalannealing or UV crosslinking, in order that it may be cured by treatingwith heat or with UV radiation, respectively.

As mentioned, the first forming material phase as first blend materialand any islands of the curable second blend material phase in the firstblend material phase are removed by dissolving in a solvent for thefirst blend material, which solvent is insolvent for the cured secondblend material. For example, if the first blend material is polystyrene,and the cured second blend material is UV-crosslinked poly(3-hexylthiophene), a suitable selective solvent for the polystyrene iscyclohexane.

After removal of the first blend material phase and any islands of thesecond blend material phase in the first blend material phase, the curedsecond blend material having a topographically highly featured surfaceis further coated, either with a second functional material in the casethat the second blend material is a first functional material, or with afirst functional material in the case that the second blend material isa second forming material. The coating is deposited over and into thepores of the laterally porous film of the cured second blend material byspin-coating from a solvent for the coating material, which solvent isinsolvent for the cured second blend material.

In the case that the second blend material is a first functionalmaterial, the coating will be a second functional material, and thus atopographically highly featured interface is formed between the twofunctional layers.

In the case that the second blend material is a second forming material,the coating will be a first functional material. After UV exposure andremoval of the second forming material and any uncured first functionalmaterial, a coating of the second functional material is deposited overand into the pores of the laterally porous film of the cured firstfunctional material by spin-coating from a solvent for the secondfunctional material, which solvent is insolvent for the cured firstfunctional material. Thus, a topographically highly featured interfaceis formed between the two functional layers.

Preferably, the first functional material forms a continuous layer overthe first electrode, or the second functional material forms acontinuous layer over the second electrode, or both, For example,materials such as amine-containing polymers, in particular polymerscomprising one or more repeat units of formulae 1-6 shown below, areknown to preferentially move to the substrate surface under certainconditions and when blended with certain materials.

wherein X, Y, A, B, C and D are independently selected from H or asubstituent group. 15 More preferably, one or more of X, Y, A, B, C andD is independently selected from the group consisting of optionallysubstituted, branched or linear alkyl, aryl, perfluoroalkyl, thioalkyl,cyano, alkoxy, heteroaryl, alkylaryl and arylalkyl groups. Mostpreferably, X, Y, A and B are C1-10 alkyl.

Particularly preferred hole transporting polymers of this type arecopolymers, in particular AB copolymers, comprising at least onetriarylamine repeat unit of formula 1-6 and an arylene repeat unit.Preferred arylene repeat units are: 1,4-phenylene repeat units asdisclosed in J. Appl. Phys. 1996, 79, 934; fluorene repeat units asdisclosed in EP 0842208; indenofluorene repeat units as disclosed in,for example, Macromolecules 2000, 33(6), 2016-2020; and spirofluorenerepeat units as disclosed in, for example, EP 0707020. Each of theserepeat units is optionally substituted. Examples of substituents includesolubilising groups such as C1-20 alkyl or alkoxy; electron withdrawinggroups such as fluorine, nitro or cyano; and substituents for increasingglass transition temperature (Tg) of the polymer.

Particularly preferred arylene repeat units comprise optionallysubstituted, 2,7-linked fluorenes, most preferably repeat units offormula (I):

wherein R′ and R2 are independently selected from hydrogen or optionallysubstituted alkyl, alkoxy, aryl, arylalkyl, heteroaryl andheteroarylalkyl. More preferably, at least one of R1 and R2 comprises anoptionally substituted C4-C20 alkyl or aryl group.

It is believed that such a continuous layer of one or both functionalmaterials over their 25 respective electrodes will improve deviceperformance by acting as a barrier to excitons and/or electrons, thuspreventing or reducing quenching, by interrupting continuous leakagepaths between the anode and cathode.

In a preferred embodiment, the first functional material is poly 3-hexylthiophene functioning as hole collecting material, the second functionalmaterial is a polyfluorene functioning as light absorbing material, andthe solvent for the polyfluorene is selected from toluene, xylene andchloroform.

In another embodiment, the first functional material is poly 3-hexylthiophene functioning as hole collecting material, the second functionalmaterial is a fullerene functioning as light absorbing material, and thesolvent for the fullerene is selected from chlorobenzene anddichlorobenzene.

If desired, the first electrode layer on the substrate may be formedwith charge transporting layer of the first functional material on thefirst electrode layer, before the blend is deposited. Preferably, thefirst electrode layer is a layer indium tin-oxide (ITO) bearing a layerof PEDOT:PSS.

The invention has applications for organic PV/photodetector devices andfor other electrical/opto-electrical devices.

At least one embodiment of the present invention will now be described,by way of example only, and with reference to the accompanying drawingsin which:

FIG. 1 is a schematic diagram of a process of phase separation accordingto a first embodiment of the present invention;

FIG. 2 is a schematic diagram of a process of phase separation accordingto a second embodiment of the present invention;

FIG. 3 is a schematic diagram of a process of phase separation accordingto a third embodiment of the present invention;

FIG. 4 is a schematic diagram of a PV device structure incorporating aninterpenetrating bi-layer according to the present invention;

FIG. 5 is an Atomic Force Microscopy image illustrating the effect ofdifferent ratios of P3HT to Polystyrene upon the structure of the P3HTfilm before having a polymer 1 formed on top;

FIG. 6 is a cross-section through the Atomic Force Microscopy image ofFIG. 5 formed from a 70/30 P3HT/PS ratio;

FIG. 7 is a cross-section through the Atomic Force Microscopy image ofFIG. 5 formed from a 30/70 P3HT/PS ratio;

FIG. 8 is an Atomic Force Microscopy image illustrating the effect ofdifferent ratios of P3HT to Polystyrene upon the structure of the P3HTfilm having a polymer 1 formed on top;

FIG. 9 is a cross-section through the Atomic Force Microscopy image ofFIG. 8 formed from a 70/30 P3HT/PS ratio;

FIG. 10 is a cross-section through the Atomic Force Microscopy image ofFIG. 8 formed from a 30/70 P3HT/PS ratio;

FIG. 11 is an Atomic Force Microscopy image of a scratch to reveal thesubstrate below before having a polymer formed on top;

FIG. 12 is a cross-section through the Atomic Force Microscopy image ofFIG. 11; and

FIG. 13 is a spectral response of a number of P3HT/Polymer 1 bilayerdevices.

The methods of the invention are further illustrated by the followingnon-limiting examples:

EXAMPLES Method 1

A polymer blend of Material I and Material 2 is spin-coated onto asubstrate, although other methods such as spray-coating, dip-coating,ink-jet printing, screen printing, gravure printing or flexographicprinting could instead be used. Two possible forms of phase separationare shown in FIGS. 1A and 2A:

FIGS. 1 and 2 illustrate the process of phase separation, selectivedissolution of Material 2, and re-filling with polymer Material 3.Materials 1 and 2 are seen to have formed a laterally phase separatedstructure in FIGS. 1A and 2A following the polymer blend deposition andphase separation process. In FIG. 2A, the materials are shown to havephase separated with functional Material 2 preferentially contactingwith the substrate, so as to form a continuous layer of Material 2 overthe substrate. In a PV device, for example, Material 2 is the donormaterial (hole acceptor and transporter) in the completed cell. Material1 is selected to provide the desired phase separated structure whenblended with Material 2 and spin-cast from solution. The phaseseparation scale is controlled, for example, by appropriate selection ofmolecular weight, solvent, solvent mix and deposition conditions.

Once formed, the phase-separated film is subjected to a process step (4)that renders Material 2 insoluble or partially insoluble, for examplethermal annealing or UV cross-linking. The film is then subjected to aprocess step (5) that selectively dissolves Material 1, leaving behind atopographically highly featured porous film of Material 2, as depictedin FIGS. 1B and 2B. Material 3 is then deposited on top of the porousfilm by a process step (6), to provide a bi-layer of functionalMaterials 2 and 3 with a topographically highly featured interface.

Suitable materials and process steps are shown below:

Example A

A blend of polystyrene (various Mw available to give correct phaseseparation) and poly 3-hexyl thiophene (P3HT) are deposited from xylenesolution followed by baking at 1800 C to cure the poly 3-hexylthiophene. Polystyrene is removed by spin rinsing the phase separatedblend with cyclohexane. Finally, Polymer I, having the structure shownbelow, is deposited from xylene solution. Heat treatment of P3HT rendersit at least partially insoluble in xylene, thus enabling deposition ofPolymer 1 from this solvent in order to form an interpenetrating film ofP3HT and Polymer 1.

The baking step may also take place after removal of polystyrene due tothe relative insolubility of P3HT in cyclohexane.

Example B

The procedure of Example A is repeated except that P3HT is provided withUV cross-linkable groups and the P3HT component of the blend layer iscured by UV treatment to cross-link the P3HT material. Curing bycross-linking renders Polymer 1 insoluble in more solvents than heattreatment of the non-crosslinked P3HT material of Example A and as suchPolymer 1 may be deposited by spin-coating from toluene or xylene orchloroform (lower viscosity).

Example C

The procedure of Example B is repeated except that the cross-linkableP3HT is crosslinked by thermal rather than UN treatment. It will beappreciated by the skilled person that a wide range of cross-linkablegroups are available, and an appropriate one may be selected accordingto the desired cross-linking conditions.

Example D

The procedure of Example B is repeated but with Polymer 1 being replacedwith PBCM (soluble substituted fullerene 1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C61) and adding chlorobenzene and dichlorobenzene tosolvents for deposition of the fullerene.

Example E

The procedure of Example C is repeated but with Polymer I being replacedwith PBCM (soluble substituted flillerene 1-(3-methoxycarbonyl)propyl-1-phenyl[6,6]C61) and adding chlorobenzene and dichlorobenzene tosolvents for deposition of the fullerene.

Method 2

Referring to FIG. 3, a blend is made of two polymer Materials 7 and 8having molecular weights so chosen such that controlled phase separationover the desired scale is achieved, and is deposited as a film on thesubstrate, as shown in FIG. 3A. First forming Material 7 is dissolvedaway. The remaining second forming Material 8 is a strong absorber inthe UV spectrum. After removal of Material 7 in process step 11, thefirst functional Material 9, which is UV curable, is deposited on thesubstrate in process step 12. Materials 8 and 9 are exposed to UVradiation from the substrate side and the phase separated UV-absorbentMaterial 8 acts as the mask so that only Material 9 in the wells iscured sufficiently to make it insoluble, as shown in FIG. 3D. Material 8and the uncured phase-separated Material 9 are then removed in processstep 13, leaving behind islands of cured Material 9 as shown in FIG. 3E.The second functional Material 10 is then deposited, in process step 14,yielding the final interpenetrating network of pure Materials 9 and 10as shown in FIG. 3F.

FIG. 4 shows a PV device structure incorporating an interpenetratingbi-layer according to the invention. A glass substrate 15 is coated withindium tin-oxide 16 and, on top of this, a layer of PEDOT:PSS 17 isspin-coated. A thin (<20 nm) layer of the hole transport material 2 isdeposited to form an anode interlayer 18. An interpenetrating network ofhole transport material 2 and electron transport layer 3 are formed inaccordance with the method of the invention. An additional cathodeinterlayer (not shown) may also be deposited. Finally the devicestructure is completed with a low-workfunction cathode 19.

Referring to FIG. 5, the different ratios of P3HT to Polystyrene producea variety of structures in the P3HT films. The 70/30 and 60/40 ratiosproduce continuous porous films, the 50/50 ratio produces films at thepercolation limit and the 40/60 and 30/70 ratios produce isolatedislands of P3HT. Although different height scales are used to displaythe images, the cross-section illustrated in FIG. 6 for 70/30 P3HT/PSand FIG. 7 for 30/70 P3HT/PS, show that the P3HT areas are all around45-50 nm higher than the substrate.

Referring to FIG. 8, the application of polymer 1 on top of the P3HTdoes not appear to have significantly, visually at least, changed thesurface topography compared to that illustrated in FIG. 5. However, asbest seen in FIGS. 9 and 10, a cross-section taken across the surface ofthe topography of FIG. 8, show that the undulations have significantlyreduced by applying Polymer 1 on top of the P3HT.

FIGS. 11 and 12 illustrate an Atomic Force Microscopy (AFM) image of ascratch in a partial P3HT film and a corresponding cross-section. FIGS.11 and 12 demonstrate that the holes left when the polystyrene wasdissolved away in the cyclohexane, do continue the majority, if not allthe way through the substrate. Accordingly, in a complete device,Polymer 1 will extend from one electrode to the other, whereas P3HT willonly be in contact with the anode.

FIG. 13 illustrates spectra from a number of P3HT/Polymer 1 bilayerdevices and the porous/partial-P3HT Polymer 1 devices based upon ExampleA as previously described. Example A was completed into a device on topof a Glass/ITO/PEDOT:PSS structure and completed with an Al or LiF/Alcathode. The maximum EQE's for the P3HT/Polymer 1 bilayer and the devicefabricated with the 70/30 P3HT/PS film are substantially the same,whereas the broadness of the peaks are different.

1. A method of preparing an opto-electronic device comprising asubstrate, a first electrode layer, a second electrode layer of oppositepolarity to said first electrode layer and, between said first andsecond electrode layers, a first functional material in interfacialcontact with a second functional material, said method comprising:forming the first electrode layer on the substrate; depositing a blendof a first forming material and a curable first functional material onsaid first electrode layer on said substrate to form a film, the firstforming material and first functional material being selected toseparate into a laterally phase separated film structure wherein thefirst forming material phase optionally contains islands of the firstfunctional material phase; treating said laterally phase separated filmstructure so as to cure said first functional material phase followed byremoving the first forming material phase and said optionally containedislands of the first functional material phase, or removing the firstforming material phase and said optionally contained islands of thefirst functional material phase from said laterally phase separated filmstructure followed by treating so as to cure said first functionalmaterial phase, to leave a cured, laterally porous film of said firstfunctional material; depositing a second functional material over andinto the pores of said cured, laterally porous film of the firstfunctional material, so as to provide a film of the second functionalmaterial over and interpenetrating with the film of the first functionalmaterial; and forming the second electrode layer over said film of thesecond functional material.
 2. A method of preparing an opto-electronicdevice comprising a substrate, a first electrode layer, a secondelectrode layer of opposite polarity to said first electrode layer and,between said first and second electrode layers, a first functionalmaterial in interfacial contact with a second functional material, saidmethod comprising: forming the first electrode layer on the substrate;depositing a blend of a first forming material and a second formingmaterial on said first electrode layer on said substrate to form a film,the first forming material and second forming material being selected toseparate into a laterally phase separated film structure wherein thefirst forming material phase optionally contains islands of the secondforming material phase; removing the first forming material phase andsaid optionally contained islands of the second forming material phase,to leave a laterally porous film of said second forming material;depositing a curable first functional material over and into the poresof said laterally porous film of the second forming material, so as toprovide a film of the first functional material over andinterpenetrating with the film of the second forming material; treatingsaid interpenetrating films of the second forming and first functionalmaterials so as to cure said first functional material phase followed byremoving the second forming material and any uncured portions of thefirst functional material, or removing the second forming material andany uncured portions of the first functional material from saidinterpenetrating films of the second forming and first functionalmaterials followed by treating so as to cure said first functionalmaterial phase, to leave a cured, laterally porous film of said firstfunctional material; depositing a second functional material over andinto the pores of said cured, laterally porous film of the firstfunctional material, so as to provide a film of the second functionalmaterial over and interpenetrating with the film of the first functionalmaterial; and forming the second electrode layer over said film of thesecond functional material.
 3. A method according to claim 2, whereinsaid second forming material is UV absorbent and said first functionalmaterial is UV-curable, and said step of treating so as to cure saidfirst functional material phase comprises the step of irradiating saidinterpenetrating films of the second forming and first functionalmaterials with UV radiation through the substrate, whereby portions ofthe first functional material exposed to the UV radiation and not maskedby the second forming material are cured and portions of the firstfunctional material unexposed to the UV radiation or masked by thesecond forming material remain uncured.
 4. A method according to claim1, comprising removing the first forming material phase and saidoptionally contained islands by dissolving in a solvent for the firstforming material, which solvent is insolvent for the cured firstfunctional material.
 5. A method according to claim 2, comprisingremoving the first forming material phase and said optionally containedislands by dissolving in a solvent for the first forming material, whichsolvent is insolvent for the second forming material, and removing thesecond forming material phase and said optionally contained islands bydissolving in a solvent for the second forming material, which solventis insolvent for the cured first functional material.
 6. A methodaccording to claim 1, wherein the device is an electroluminescent orOLED device; the first functional material is a charge transportingmaterial; the second functional material is an electroluminescentmaterial; the first electrode layer is the anode and the secondelectrode layer is the cathode.
 7. A method according to claim 1,wherein the device is an photovoltaic device; the first functionalmaterial is a hole transporting material; the second functional materialis an electron transporting material; the first electrode layer is theanode and the second electrode layer is the cathode.
 8. A methodaccording to claim 1, wherein the curable first functional material iscurable by thermal annealing and/or UV-cross-linking, and is cured bytreating with heat and/or UV radiation.
 9. A method according to claim1, wherein the first forming material is polystyrene.
 10. A methodaccording to claim 9, wherein the solvent is cyclohexane.
 11. A methodaccording to claim 1, comprising depositing the blend by a techniqueselected from the group consisting of spin-coating, spray-coating,dip-coating, inkjet printing, screen printing, gravure printing, andflexographic printing.
 12. A method according to claim 1, comprisingdepositing the second functional material over and into the pores of thelaterally porous film of the cured first functional material by atechnique selected from the group consisting of spin-coating,spray-coating, dip-coating, inkjet printing, screen printing, gravureprinting, and flexographic printing from a solvent for the secondfunctional material, which solvent is insolvent for the cured firstfunctional material.
 13. A method according to claim 2, comprisingdepositing the first functional material over and into the pores of thelaterally porous film of the second forming material by a techniqueselected from the group consisting of spin-coating, spray-coating,dip-coating, inkjet printing, screen printing, gravure printing, andflexographic printing from a solvent for the first functional material,which solvent is insolvent for the second forming material.
 14. A methodaccording to claim 1, wherein the first functional material is poly3-hexyl thiophene functioning as hole collecting material, the secondfunctional material is a polyfluorene functioning as an electroncollecting material, and the solvent for the polyfluorene is selectedfrom the group consisting of toluene, xylene and chloroform.
 15. Amethod according to claim 1, wherein the first functional material ispoly 3-hexyl thiophene functioning as hole collecting material, thesecond functional material is a fullerene functioning as an electroncollecting material, and the solvent for the fullerene is selected fromthe group consisting of chlorobenzene and dichlorobenzene.
 16. A methodaccording to claim 14, wherein one or both of the first and secondfunctional materials is or are a light absorbing material.
 17. A methodaccording to claim 1, further comprising forming a charge transportinglayer of said first functional material on the first electrode layer onthe substrate, before said blend is deposited.
 18. A method according toclaim 1, wherein the first electrode layer is a layer indium tin-oxide(ITO) bearing a layer of PEDOT:PSS.
 19. An opto-electronic devicecomprising a substrate, a first electrode layer, a second electrodelayer of opposite polarity to said first electrode layer and, betweensaid first and second electrode layers, a first functional material ininterfacial contact with a second functional material, wherein the firstfunctional material has the structure of a laterally porous film and thesecond functional material is a film disposed over and interpenetratingwith the film of the first functional material.
 20. An opto-electronicdevice according to claim 19, wherein the device is anelectroluminescent or OLED device; the first functional material is acharge transporting material; the second functional material is anelectroluminescent material; the first electrode layer is the anode andthe second electrode layer is the cathode.
 21. An opto-electronic deviceaccording to claim 19, wherein the device is an photovoltaic device; thefirst functional material is a hole transporting material; the secondfunctional material is an electron transporting material; the firstelectrode layer is the anode and the second electrode layer is thecathode.
 22. An opto-electronic device according to claim 21, whereinthe first functional material is poly 3-hexyl thiophene functioning ashole collecting material, and the second functional material is selectedfrom a polyfluorene and/or a fullerene functioning as an electroncollecting material.
 23. An opto-electronic device according to claim22, wherein one or both of the first and second functional materials isor are a light absorbing material.
 24. An opto-electronic deviceaccording to claim 19 further comprising an interlayer of said firstfunctional material disposed between the first electrode layer on thesubstrate and the interpenetrating films of the first and secondfunctional materials.
 25. An opto-electronic device according to claim19, wherein the first electrode layer is a layer indium tin-oxide (ITO)bearing a layer of PEDOT:PSS.
 26. A method according to claim 2, whereinthe device is an electroluminescent or OLED device; the first functionalmaterial is a charge transporting material; the second functionalmaterial is an electroluminescent material; the first electrode layer isthe anode and the second electrode layer is the cathode.
 27. A methodaccording to claim 2, wherein the device is an photovoltaic device; thefirst functional material is a hole transporting material; the secondfunctional material is an electron transporting material; the firstelectrode layer is the anode and the second electrode layer is thecathode.
 28. A method according to claim 2, wherein the curable firstfunctional material is curable by thermal annealing and/orUV-cross-linking, and is cured by treating with heat and/or UVradiation.
 29. A method according to claim 2, wherein the first formingmaterial is polystyrene.
 30. A method according to claim 29, wherein thesolvent is cyclohexane.
 31. A method according to claim 2, comprisingdepositing the blend by a technique selected from the group consistingof spin-coating, spray-coating, dip-coating, inkjet printing, screenprinting, gravure printing, and flexographic printing.
 32. A methodaccording to claim 2, comprising depositing the second functionalmaterial over and into the pores of the laterally porous film of thecured first functional material by a technique selected from the groupconsisting of spin-coating, spray-coating, dip-coating, inkjet printing,screen printing, gravure printing, and flexographic printing from asolvent for the second functional material, which solvent is insolventfor the cured first functional material.
 33. A method according to claim2, wherein the first functional material is poly 3-hexyl thiophenefunctioning as hole collecting material, the second functional materialis a polyfluorene functioning as an electron collecting material, andthe solvent for the polyfluorene is selected from the group consistingof toluene, xylene and chloroform.
 34. A method according to claim 2,wherein the first functional material is poly 3-hexyl thiophenefunctioning as hole collecting material, the second functional materialis a fullerene functioning as an electron collecting material, and thesolvent for the fullerene is selected from the group consisting ofchlorobenzene and dichlorobenzene.
 35. A method according to claim 33,wherein one or both of the first and second functional materials is orare a light absorbing material.
 36. A method according to claim 2,further comprising forming a charge transporting layer of said firstfunctional material on the first electrode layer on the substrate,before said blend is deposited.
 37. A method according to claim 2,wherein the first electrode layer is a layer indium tin-oxide (ITO)bearing a layer of PEDOT:PSS.